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Measurements of Radical Reactivity with an Imine, (CF3)2CNH: Rate Constants for Chlorine Atoms and Hydroxyl Radicals
1Department of Chemistry and Center for Advanced Scientific Computing and Modeling, University of North Texas, 1155 Union Circle #305070, Denton, TX 76203, USA.
Abstract:
The rate constant kOH for the reaction of 1,1,1,3,3,3-hexafluoroprop-2-imine with OH radicals was measured relative to two reference compounds, CH3F and CH3CHF2, to be kOH = (4.2 ± 1.1) × 10-14 cm3 molecule-1 s-1 at 295 K. This implies an atmospheric lifetime with respect to consumption by OH of 0.75 years. Reaction with Cl atoms yielded kCl = (7.9 ± 1.7) × 10-16 cm3 molecule-1 s-1 at 295 K, and reaction with O3 has an upper limit of kO3 < 4 × 10-23 cm3 molecule-1 s-1, so that the atmospheric consumption by Cl and O3 is negligibly slow. Absolute infrared cross sections of the imine yield a radiative efficiency of 0.34 W m-2 ppb-1, which is corrected to 0.23 W m-2 ppb-1 for the effects of atmospheric lifetime. The imine's corresponding 100-year global warming potential is 64 ± 19. This value is an upper limit, given that heterogenous atmospheric removal paths, such as hydrolysis in water droplets, are not included.
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